While current understanding of chemical reactivity often makes it possible to design or choose an appropriate catalyst for a new molecular transformation, achieving adequate reactivity is often a cumbersome process. Typically, many iterations involving methodical manipulation of catalyst substructure, analysis of the resulting effect and redesign, are required. In an effort to facilitate this recursive catalyst optimization process, various research groups have started to use the techniques of combinatorial chemistry and solid phase synthesis to rapidly produce large numbers of potential catalysts. See, e.g., F. Menger et al., J. Org. Chem. 60, 6666 (1995); G. Liu and J. Ellman, J. Org. Chem. 60, 7712 (1995); K. Burgess et al., Angew. Chem. Int. Ed. Engl. 35, 220 (1996); B. Cole et al., Angew. Chem. Int. Ed. Engl. 35, 1668 (1996). Unfortunately, despite progress in evaluating the thermodynamics of equilibrium processes on solid support, methods for assessing the kinetics of reactions involving polymer-bound reagents have not been available. This circumstance has prevented the analysis of very large libraries (10.sup.4 -10.sup.6 members) as screening for organic catalysts requires an individual assay for each member of a catalyst library.
According to the observation that most chemical reactions have a non-zero AH, temperature has been used to survey the progress of catalytic reactions. Since all catalysts in a library assay are evaluated under the same reaction conditions, the most active catalyst will exhibit the largest temperature change (.DELTA.T.about.turnover frequency.multidot..DELTA.H). Moates et al. applied this principle for the parallel evaluation of the ignition temperatures of 16 metal-doped alumina pellets in the presence of H.sub.2 and O.sub.2 at elevated temperatures in gas phase. F. Moates et al., Ind. Eng. Chem. Res. 35, 4801-4803 (1996). To date, however, there has not been a way to apply such techniques to the analysis of polymer-bound catalyst libraries for solution-phase chemical reactions.